Substituted derivatives of benzoquinone as bodying agents for oils



Patented Mar. 23, 1954 UNITED STATES PATENT OFFICE SUBSTITUTEDDERIVATIVES OF BENZO- QUINONE AS BODYING AGENTS FOB OILS No Drawing.Application August 8, 1951, Serial No. 240,984

21 Claims. 1

This invention relatesto the use of benzoquinone derivatives ascatalytic agents for the treatment of vegetable oils so as to obtainproducts of increased viscosity or body which are useful in theprotective coating art.

One of the most time consuming operations in the manufacture of paints,varnishes, and other related coating materials has been the preparationof partially polymerized or bodied oils of increased viscosity, ascompared to the viscosity of the starting material. The viscosity ofvegetable oils can, in many instances, be increased to the desiredextent by heating such oils to high temperatures under variousconditions. However, such heat-bodying processes are subject to severaldisadvantages as, for example, the following:

(A) Long reaction period,

(B) Darkening in color to an objectionable extent caused by prolongedheating, and

(C) Decomposition of the oil at high temperatures.

The polymerization or bodying of oils can be promoted or accelerated bythe presence of many catalytic agents, e. g. metals, salts,halanhydrides, numerous organic compounds, etc. However, many of theseagents cause an excessive darkening in the color of oil, therebyrendering the oil of diminished value for many of the purposes for whichit may be intended.

U. S. Patent 2,213,935, dated September 3, 1940, discloses theemployment of polycyclic condensed ring systems containing nuclear oxosubstituents as catalysts in the heat bodying of oils. It is stated thatthe employment of these catalytic agents in small concentrations bringsabout the desired polymerization of various oils at an increased speedwithout color deterioration. However, such polycyclic condensed ring oxoderivatives are relatively expensive as compared with the simpler,non-ring condensed quinone catalysts employed in accordance with ourinvention. U. S. 2,298,915, dated October 13, 1942, also discloses theemployment of organic cyclic compounds containing a condensed ringsystem in the molecule which are capable of modifying the physicalproperties of vegetable oils, for example, Z-amino-anthraquinone.

In addition to U. S. 2,298,915, mentioned above, there are at leasteight other patents issued to the same inventor, namely Laszlo Auer, allof which relate to the modification or catalyzing of various materialsincluding vegetable oils whereby a product of increased viscosity can beeb- 2 tained. These patents include 2,213,944,. dated September 10,1940; 2,234,949, dated March 18, 1941; 2,344,666, dated June 10, 1941;2,298,270, 2,298,271, 2,298,918, 2,298,919 (the latter four patentsbeing dated October 13, 1942); and 2,322,106, dated June 15, 1943. Inaddition to Auers Patent No. 2,234,949, which relates to the employmentof aromatic amines, a patent to W.

C. Arsem, No. 1,760,535, dated May 2'7, 1930, makes a similardisclosure.

None of the prior art mentioned herein-above discloses the employment ofderivatives of benzoquinone for the bodying of vegetable oils. Fur:thermore, none of this art discloses the employment of more than a verylimited number of 0x0 derivatives of particular types as bodying agents.Examples of the 0x0 derivatives disclosed include p,pdiamino-diphenylbenzophenone, 1,4- diaminoanthraquinone, ureaderivatives, such as diaminodiaryl urea compounds, and similarcompounds, none of which are oxo-substituted alicyclic derivatives suchas derivatives of benzequinone, which, from the point of view of theiralicyclic oxo-substituted structure, could be termed2,5-cyclohexadiene-1,4-dione derivatives.

We have now found that derivatives of benzoquinone having the followingformula:

wherein R1 represents a substituent selected from those consisting ofalkyl radicals, substituted alkyl radicals, alkoxy radicals, arylradicals, substituted aryl radicals, aryloxy radicals, alkylaminoradicals, arylamino radicals, an amino radical, a chlorine atom, abromine atom and 9. nitro radical, and R2, R3 and R4 each represents ahydrogen atom or any substituent selected from those which R1 canrepresent. The substituents on the alkyl and, aryl radicals include analkyl radical, an aryl radical, a nitro radical, an amino radical, ahalogen atom, etc. The nitrogen atom of the alkylamino and arylaminoradicals can be tertiary, as well as secondary, e. g. dialkylamino,diarylamino and arylalkylamino.

Examples of the benzoquinone derivatives which fall within the scope ofthe above-defined formula and which can be employed in accordance withour invention include, p-nitrophenylqulnone, 2,5-dioctylquinone,phenylquinone, 2,5?

3 (ii n butylaminoquinone, 2,5-dianilinoduinone, phenyltrichloroquinone,2,S-di-tert-butylquinone, 2,5-dimethoxyquinone, etc. It is believed thatthe prior art clearly indicates the broad nature of the substituefits'which can be employed, for examplaa study of the patents referred toabove clearly indicates that many other substituents than those setforth under the above defined formula would no doubt result insubstituted quinone derivatives having worthwhile bodying properties.

It is an object of our invention to provide a new type of catalyticbodyirigagents consisting of the substituted benzoquinoiie derivatives.It is a further object of our invention to provide a process for thebodying of vegetable oils em ploying substituted benzoquinonederivatives; Another object of our invention is to provide a process forproducing bodied oils in an economi cally advantageous manner. A furtherobject is to proviide' a methodffor producing highly satisfactorycoating materials, such as paints and V9; ishes wherein the oilconstituents of these eoatingmaterials are bodied byth'e employment ofderivatives of benzoquinone. je'e "will become apparenthereinafter.-Examples of' the oils which can be bodied in acccr'darice with thisinvention include vegetable oil,"'etc.' In addition to the vegetableoils, esters of soya bean oil, poppyseed 'o'il, sunflower oil,cottonseed a r-corn oil, olive oil, castor oil, hempseed oil, etc. Inaddition to the vegetableoils, esters of the fatty acids whichare'present in any of these oils, other-than the'natur'al' g'lyceridescan also be employed. In'the preparation'oi coating mate rials,vegetable oils are generally employed; How-.

ever, any of the oils subject to bodyin'g processes can be employedaccordance withthe process of" this invention. f

""Thevegetable oils can be classified as follows:

mime 0.1

Linseed oil 111x 5 il Peril a. il

emiyin 1 Popp eed oil. Rapeseed oil Sunflower oil Soya bean oil Walnutoil Pineseed oil Non-drying oils:

Olive oil Corn oil Cottonseed oil c eeen l In accordance with theinvention, the oils referredto may be treated individually or they maybe treatedin mixtures containing more than one ofthe'se oils. "Suchmixtures mayjalso contain other materials such as plasticizers,synthetic resins, natural resins, fatty oils of: synthetic origin, etc.i The oils can be bodied in accordance with this invention byintroducing the substituted benzoquinone derivatives into the unbodiedoil" and then heating to an elevated temperature or the oil can be firstheated and the 'benzloqui'nonederivative added'to the hot oil. Ifdesired,"the oil can be partially bodied in anelevalted temperatureprior to the introduction of; the substituted benzoquinone derivative.Advantageouslythe'oil whichis tq be bodied is heated with the'subse.qiie'nt addition of benzoquinone derivative;

Still further 6biliary agents can also be employed if desired. Moreoverthe oil to be bodied can also be in admixture with other materialsduring the bodying process. Such additional materials can includeplasticizers and "ether inpdiiying ingredients.

1 Various proportions of the substituted benzoquinone derivatives can beemployed in effecting the bodying of the oil. Generally speaking aquantity of this catalyst on the order of 1% can be employed.'l-Iewever, depending upon the degree of bodying desired and the speedwith which the bodying is to be accomplished, the concentration of thesubstituted benzoquinone derivative can be varied from a small fractionof 1% up to 10% or more by weight of the oil being bodied,Advantageously from 0.1% to 5% of the .benzoduinone derivative isemployed. Two or more of such derivatives can also be advant'a'gebu'sly'"employed together in which case the total concentration of suchcatalysts is advantageously from aboutO.1% to 'about5%.

The temperature at which the bodying processis conducted is alsodependent upon similar factors" as the concentration of the subistituted benzoquinone derivatives being employed. Higher temperaturesproduce'more rapid bodying but as the temperature is increased some'discolorationmay occur." Temperatures which can be employed also dependupon the nature of the oil being bodied inasmuch as some oils are moresusceptible to decomposition than others. Advantageously a temperatureoffrom about 500? F. tc'about 650 F.' is generally satisfactory.However, higher or lower temperatures can also be employed, dependingupon the conditions as indicated. Most advantageously a temperature fromabout 535 F. to about 625 F. is employed in accordance with modernpractice in the bodying. of th? oils. t

Inasmuch as the primary feature of this invention resides in theprovision of anew class or oil bodying' agents, namely thesubstitutedbenzo' quinone derivatives, it is not believednecessary tqndu se. i a engthy es r ptiono he ario medifiqa i n Q hqse oc du es whih. can be mplo d. n the bodying oi i em lo n such ubs i ted benzouinoneder vati es, The error; a t, discussed abo e. qee he w ib th Qtherpr r art. i s merou ex m lesa i esc ibesvan: 0115 me e Qi ayinetherqceciures. hichcen beeinployed.

Th ell r .e:v exampl s will se ve o urth illustrate the nvention. Inthese examples 1i 9 tea e y ca ii f belassde bed above- Tw t -ene, erate. xampl s a e se mm, Q QW: n each, xam le beak cqnt inine 0.

rams w seed-.0 1 a smplq ede 5 am mple nf- Oil mp o ed f a iven hencequinone derivative were drawn from a larger quan y Qf aw lin e oilwbich'w'ass un orm ua y so t a t e e ul s oulde c mpared it a n l am leim-gr ms. qfi he ame, eweil; wherein no benzoquinone derivativewaspresent.

The control-datatabulatedbelow is in additiontq e 2, m les-0i b di d dQniam a Q tar lyst. The beakers containing 50ig rams ofrawlinseedoilwere heated to. 5595B, and the benz qi quinone derivativewasadded sodas to. result in.

aconcentration of 0.5% in one seriesoi examples,

1.0% in. anotherseries. of examples, and.1.5%, in.

a third series of;examples, for. each ofzthe benzoquinone derivativeslisted below. Concentrations are based on the weight of the rawlinseed-oil.

Heating was continued 'for two hours'with oci l be ause it desn eicasional stirring, maintaining a temperature of approximately 550 F.After this, the bodied oil was cooled to 250 C. in each instance and theviscosity was determined using Gardner-Holdt viscosity tubes as astandard. In order to avoid repetition in stating the procedure employedin each of the 21 examples employing substituted benzoquinonederivatives, the following tabulation is presented, wherein theviscosities are reported to the nearest letter on the Gardner-Holdt 0(G. H.) viscosity scale and also in poises (P.).

Results obtained in the heat bodying of linseed oil in the presence ofbeneoquinone derivatives Concentration 0% 0.5% 1.0%

G. H. I. o. H. P. G. H. P. G.H. I.

Bodying Agents:

p-nitrophenylquiuone 0 3.7 U 6.27 V 8. 84 W 10.7

2,5-dioctylquinonc M O 3. 7 K 2. 75 T 5. 50

phenylquinone O 3. 7 K 2. 75 O 3. 7 T 5. 5

2,5-di-n-butylaminoquinou K 2.75 S 5.00 V 8. 84 Y 17.6

2,5-di-anilinoquinone K 2. 75 U 6.27 W 10.7 2 22.7

phenyltrichloroquinona.. K 2.75 V 8. 84 U 0. 27 V 8.84

2,5-di-te1t-butylquinone K 2. 75 S 5. 00

2,5-dimethoxyquinone K 2.75 V 8. 84 X 12.9 Z 27 The above 21 examplesresulted in the prepare 6. A process as defined in claim 5 wherein thetion of bodied oils of various degrees of clarity. temperature range isfrom about 535 F. to about The benzoquinone derivatives wherein the sub-625 F. and the benzoquinone derivative is presstituent group or groupswas alkyl, alkoxy, or an 30 ent to the extent of from about 0.1% toabout unsubstituted aryl group, resulted in the produc- 5%. tion ofclear bodied oils. The benzoquinone de- 7. A process for bodyingvegetable oils which rivatives which contained a substituent groupcomprises heating a vegetable oil in the presence containing the nitro,amino, and chloro substitof from about 0.1% to about 10% by weight ofuents resulted in bodied oils which were satisthe oil of a substitutedbenzoquinone derivative factory for use in coating materials; however,wherein the substituent is a hydrocarbon radthese bodied oils weredarker in nature than the ical. other bodied oils. Thus, the bestresults can gen- 8. A process as defined in claim '7 wherein the erallybe obtained employing benzoquinone desubstituted benzoquinone derivativeis 2,5-dioctylrivatives which contain substituents which are 40 quinone.hydrocarbon or alkoxy radicals instead of radicals 9. A process asdefined in claim '7 wherein the of acids or amine radicals. substitutedbenzoquinone derivative is phenyl- It is clearly evident that other oilscan be emquinone. ployed advantageously in accordance with the 10. Aprocess as defined in claim 7 wherein above described process whereinlinseed oil was the substituted benzoquinone derivative is2,5-diemployed, and that other temperatures and contert-butylquinone,centrations as well as periods of heating can ad- 11. A process asdefined in claim 7 wherein the vantageously be employed to producesatisfacsubstituted benzoquinone derivative is 2,5-di tory products.Thus, sunflower oil can be heated methoxyquinone. at 5 p y ng 4% of2,5-d yq 12. A process for bodying vegetable oils which as the catalyst;soy bean oil can be heated at 625 comprises heating a vegetable oil to atemperature F. e ploy py q at a Concentration 0f of from about 500 F. toabout 650 F. in the pres- 5%; perilla oil can be heated at a tempe a e oence of from about 0.1% to about 10% by weight 535 employing D py q aaco of the oil of a substituted benzoquinone derivacentration of 3%. Thebodied oils so obtained tiv having the formula: can be employed in thepreparation of coating 0 materials. it

What we claim as our invention and desire to secure by Letters Patent ofthe United States is: n-O (fi-Rr 1. A process for preparing bodiedvegetable oils which comprises heating a vegetable oil at an elevatedtemperature in the presence of a subl stituted benzoquinone derivative.A

A for preparmg bowed vegetable 0118 wherein R1 represents a substituentselected from Whlch compnses heatmg afivegetable a those consisting ofalkyl radicals, R5 substituted i below that atyhlch substfamlal t alkylradicals, alkoxy radicals, aryl radicals, R5 posltlon takes q mlxmgthergwlth cttaliftm substituted aryl radicals, aryloxy radicals,alkylamount of a substituted benzoquinone derivative, amino radicalsarylamino radicals, an amino and continuing the heating until the oilbecomes ical, a chlorine atom a bromine atom and a nitro bodiedradical,wherein R5 represents a group selected 3. A process for preparing bodiedvegetable oils which comprises heating a mixture comprising a vegetableoil and a catalytic amount of a substituted benzoquinone derivative to atemperature from those consisting of alkyl, aryl, nitro and aminoradicals and chlorine and bromine atoms, and R2, R3 and R4. eachrepresents a hydrogen atom or any substituent selected from those whichHi can represent.

13. A process as defined in claim 11 wherein the temperature is fromabout 535 F. to about 625 F. and the concentration of the substitutedbenzoquinone derivative is from about 0.1% to about 5% based on theweight of the oil.

14. A process as defined in claim 13 wherein the substitutedbenzoquinone derivative is 2,5-dioctylquinone.

15. A process as defined in claim 13 wherein the substitutedbenzoquinone derivative is phenylquinone.

16. A process as defined in claim 13 wherein the substitutedbenzoquinone derivative is 2,5-d1- tertbutylquinone.

1'7. A process as defined in claim 13 wherein the substitutedbenzoquinone derivative is 2,5-dimethoxyquinone.

18. A process as defined in claim 13 wherein the oil is linseed oil andthe substituted benzoquinone derivative is 2,5-dioctylquinone.

19. A process as defined in claim 13 wherein the Oil is linseed oil andthe substituted benzequinone derivative is phenylquinone.

20. A process as defined in claim 13 wherein the oil is linseed oil andthe substituted benzoquinone derivative is 2,5-di-tert-buty1quinone.

.21.. A process as defined in claim 13 wherein the oil is linseed oiland the substituted benzoquinone derivative is 2,5-dimethoxyquinone.

DE WALT S. YOUNG. LEE G. DAVY.

References Cited in the file of this patent UNITED STATES PATENTS

1. A PROCESS FOR PREPARING BODIED VEGETABLE OILS WHICH COMPRISES HEATINGA VEGETABLE OIL AT AN ELEVATED TEMPERATURE IN THE PRESENCE OF ASUBSTITUTED BENZOQUINONE DERIVATIVE.